TY - JOUR A1 - Silva, C.P. A1 - Lima, D.L.D. A1 - Schneider, Rudolf A1 - Otero, M. A1 - Esteves, V.I. T1 - Development of ELISA methodologies for the direct determination of 17beta-estradiol and 17alpha-ethinylestraydiol in complex aqueous matrices JF - Journal of environmental management N2 - This study comprises the development of enzyme-linked immunosorbent assays (ELISAs) for the quantification of 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) in complex aqueous matrices without any sample clean-up procedures. Salinity and dissolved organic matter were selected as potential interfering agents in the analysis of E2 and EE2. The optimization was performed in order to (i) overcome matrix effects, and to (ii) increase sensitivity. The addition of a sample buffer containing bovine serum albumin (BSA) prior to the sample was found to decrease the influence of matrix effects. Moreover, adjustments of this buffer's pH together with the optimization of tracer (T) dilution and incubation time were undertaken in order to lower the quantification range. The optimized methods allowed the quantification of E2 and EE2 in the ranges 0.03–200 µg L-1 and 0.02–10 µg L-1, respectively. The assays were applied to real aqueous samples. It was possible to do a first approach to the levels of E2 in Portuguese surface and waste waters; however, it was not feasible to detect EE2 in the samples tested. KW - Enzyme-linked immunosorbent assay KW - Endocrine disrupting compounds KW - 17beta-Estradiol KW - 17alpha-Ethinylestradiol KW - Surface water KW - Wastewater PY - 2013 DO - https://doi.org/10.1016/j.jenvman.2013.03.041 SN - 0301-4797 SN - 1095-8630 VL - 124 SP - 121 EP - 127 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-28516 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Silva, C.P. A1 - Lima, D.L.D. A1 - Schneider, Rudolf A1 - Otero, M. A1 - Esteves, V.I. T1 - Evaluation of the anthropogenic input of caffeine in surface waters of the north and center of Portugal by ELISA JF - The science of the total environment N2 - This study comprises the development of an enzyme-linked immunosorbent assay (ELISA) for the quantification of caffeine in complex aqueous matrices without any sample clean-up procedure. Salinity and dissolved organic matter were selected as potential interfering agents. The addition of a sample buffer containing bovine serum albumin (BSA) prior to the sample was found to decrease the influence of those interfering agents. The working range of the developed method was 0.1–100 µg L- 1. Quantification of caffeine was possible in 43 out of 51 real aqueous samples, at values between < LOD and 15 µg L- 1. Results correlate well with those obtained by LC–MS/MS. To the best of our knowledge this is the first study dealing with the quantification of caffeine in Portugal's surface waters. KW - Caffeine KW - Surface water KW - ELISA KW - Anthropogenic markers KW - Koffein KW - Eintrag KW - Oberflächenwasser KW - Gewässer KW - Abwasser KW - Antikörper KW - Immunoassay PY - 2014 DO - https://doi.org/10.1016/j.scitotenv.2014.01.120 SN - 0048-9697 VL - 479-480 SP - 227 EP - 232 PB - Elsevier CY - Amsterdam AN - OPUS4-30450 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Silva, C. P. A1 - Carvalho, T. A1 - Schneider, Rudolf A1 - Esteves, V. I. A1 - Lima, D. L. D. T1 - ELISA as an effective tool to determine spatial and seasonal occurrence of emerging contaminants in the aquatic environment JF - Analytical Methods N2 - During the last two decades, studies related to the occurrence and fate of emerging contaminants in the aquatic environment have received great attention from the international scientific community. The monitoring of the presence of these compounds is particularly important since they are known to induce adverse effects in aquatic environments, even at extremely low concentrations. This work aimed to apply a simple and effective methodology, such as enzyme-linked immunosorbent assay (ELISA), in the monitoring of 17a-ethinylestradiol (EE2) and 17b-estradiol (E2) (a synthetic and a natural hormone, respectively), carbamazepine (CBZ, an antiepileptic), cetirizine (CET, an antihistamine) and caffeine (CAF, a stimulant) in water matrices with differing salinity and organic matter contents. ELISA was proven to be a valid and practical tool, especially for screening purposes in contrast to traditional chromatographic techniques which are prohibitively expensive for an application on a broader base. The main originality of this work was to establish seasonal and spatial effects on the occurrence of the referred contaminants by using the effectiveness of ELISA to screen those compounds in samples with different characteristics. This work reports both the seasonal and spatial quantification of the referred contaminants in the aquatic environment of the central region of Portugal, with concentrations ranging as follows: 5–87 ng L-1, for E2, 2–17 ng L-1, for EE2, 10–1290 ng L-1, for CBZ, 10–190 ng L-1, for CET, and 62–6400 ng L-1, for CAF. KW - Estrogen KW - Estradiol KW - Ethinylestradiol KW - Carbamazepine KW - Portugal KW - Wasser PY - 2020 DO - https://doi.org/10.1039/D0AY00426J SN - 1759-9679 VL - 12 IS - 19 SP - 2517 EP - 2526 PB - Royal Society of Chemistry RSC CY - London AN - OPUS4-51340 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Teixiera, M. A1 - Almeida, Ângela A1 - Calisto, V. A1 - Esteves, V. I. A1 - Wrona, F. J. A1 - Soares, A. M. V. M. A1 - Figueira, E. A1 - Freitas, R. T1 - Toxic effects of the antihistamine cetirizine in mussel Mytilus galloprovincialis JF - WATER RESEARCH N2 - Recent studies have become increasingly focused on the assessment of pharmaceuticals occurrence in aquatic ecosystems, however the potential toxicity to non-target organisms is still largely unknown. The antihistamine cetirizine is a commonly used pharmaceutical, already detected in surface waters of marine aquatic systems worldwide. In the present study Mytilus galloprovincialis mussels were exposed to a range of cetirizine concentrations (0.3, 3.0, 6.0 and 12.0 mu/L), resembling moderate to highly contaminated areas, over 28 days. The responses of different biochemical markers were evaluated in mussels whole soft tissue, and included energy-related parameters (glycogen content, GLY; protein content, PROT; electron transport system activity, ETS), and oxidative stress markers (superoxide dismutase activity, SOD; catalase activity, CAT; glutathione S-transferases activity, GSTs; lipid peroxidation levels, LPO; reduced (GSH) and oxidized (GSSG) glutathione content). The results obtained demonstrated that with the increase of exposure concentrations mussels tended to increase their energy reserves and maintain their metabolic potential, which was significantly higher only at the highest concentration. Our findings clearly revealed that cetirizine inhibited the activity of GSTs and although induced the activity of antioxidant enzymes (SOD and CAT) mussels were not able to prevent cellular damages observed through the increase of LPO associated to the increase of exposure concentrations. Thus, this study confirmed that cetirizine induces toxic effects in Mytilus galloprovincialis, which, considering their trophic relevance, wide use as bioindicator and wide spatial distribution of this species, can result in ecological and economic negative impacts at a large scale. KW - Bivalves KW - Biomarkers KW - Oxidative Stress PY - 2017 DO - https://doi.org/10.1016/j.watres.2017.02.032 SN - 0043-1354 VL - 114 SP - 316 EP - 326 AN - OPUS4-43302 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Oliveira, P. A1 - Almeida, Ângela A1 - Calisto, V. A1 - Esteves, V. I. A1 - Wrona, F. J. A1 - Soares, A. M. V. M. A1 - Figueira, E. A1 - Freitas, R. T1 - Physiological and biochemical alterations induced in the mussel Mytilus galloprovincialis after short and long-term exposure to carbamazepine JF - Water Research N2 - The bivalve Mytilus galloprovincialis collected in the Ria de Aveiro, was selected to evaluate the acute and chronic effects of carbamazepine (CBZ) at environmentally relevant concentrations. CBZ is an antiepileptic drug widely found in the aquatic environment with toxic effects to inhabiting organisms. However, few studies evaluated the acute and chronic toxicity of this drug. The experiment was performed 'by exposing mussels to 0.0, 0.3, 3.0, 6.0 and 9.0 CBZ mu g/L, for 96 h and 28 days. To assess the toxicity of the drug, a battery of biomarkers related to mussels general physiological health status and oxidative stress was applied. CBZ was quantified in mussel tissues by an Enzyme-Linked Immunosorbent Assay (ELISA). The results obtained show that CBZ did not induce oxidative stress. However, our findings,demonstrated that the drug was taken up by mussels even though presenting low bioconcentration factor (BCF) values (up to 2.2). Furthermore, our results demonstrated that after a chronic exposure the physiological parameters, namely the condition and gonadosomatic indices, were negatively affected which may impair organisms' reproductive capacity with consequences to population sustainability. KW - Pharmaceuticals KW - Bivalves KW - Oxidative Stress PY - 2017 DO - https://doi.org/10.1016/j.watres.2017.03.052 SN - 0043-1354 VL - 117 SP - 102 EP - 114 PB - Elsevier Ltd. AN - OPUS4-43304 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Fernandez, L. A1 - Borzecka, W. A1 - Lin, Z. A1 - Huvaere, K. A1 - Esteves, V. I. A1 - Cunha, A. A1 - Tome, J. P. C. T1 - Nanomagnet-photosensitizer hybrid materials for the degradation of 17 beta-estradiol in batch and flow modes JF - Dyes and Pigments N2 - The preparation of porphyrins and phthalocyanines covalently attached onto nanostructured magnetic supports consisting of magnetite nanoparticles coated with an amorphous silica shell is reported. The easy recovery of these heterogeneous photocatalysts, just by applying an external magnetic field, allows their reuse in multiple treatment cycles. The photocatalytic activity of the non-immobilized photosensitizers and the obtained hybrid materials was evaluated in the degradation of 17 beta-estradiol, as a model organic pollutant present in water, using batch and flow mode treatment systems, assisted by visible light radiation (4 mW cm(-2)). The flow mode system potentiated the photocatalytic capacity of these novel hybrid materials. In order to improve the process, further studies based on different photocatalyst concentration and pH conditions were performed. Reuse capacity of these materials was investigated upon three photocatalytic cycles. KW - Photodegradation KW - 17 beta-Estradiol KW - Porphyrin PY - 2017 DO - https://doi.org/10.1016/j.dyepig.2017.04.010 SN - 0143-7208 VL - 142 SP - 535 EP - 543 PB - Elsevier Ltd. AN - OPUS4-43308 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Almeida, Ângela A1 - Calisto, V. A1 - Esteves, V.I. A1 - Soares, A.M.V.M. A1 - Figueira, E. A1 - Freitas, R. T1 - Toxicity associated to uptake and depuration of carbamazepine in the clam Scrobicularia plana under a chronic exposure JF - SCIENCE OF THE TOTAL ENVIRONMENT N2 - Carbamazepine (CBZ) is an antiepileptic drug commonly detected in aquatic systems, with toxic effects to inhabiting organisms. Limited information is known on stress response biomarkers associated to bioconcentration and depuration of CBZ in aquatic organisms. Moreover, few studies addressed if the response and recovery of organisms to a contaminant can change when they are collected in a contaminated site. This study intended to understand the bioconcentration and depuration of CBZ combined with its toxicological impact in Scrobicularia plana clams collected from two contrasting areas (MIRA, Mira channel, non-contaminated and LAR, Laranjo bay, arithropogenically impacted) from the Ria de Aveiro (Portugal). The clams were exposed for 14 days to environmentally relevant CBZ concentrations (0.0, 4.0 and 8.0 mu g/L), followed by a 14 day depuration period. CBZ concentrations in S. plana tissues were rapidly bioconcentrated during the exposure period. In the depuration period CBZ was eliminated, in some extent. The main toxic effects occurred at the highest concentration (8.0 mu g/L) after 14 days of exposure in which the clams from LAR accumulated ahigher CBZ concentration (LAR: similar to 10 ng/g FW) than clams from MIRA (MIRA: similar to 7 ng/g FW). LAR clams exhibited higher oxidative damage at this concentration, demonstrated by higher LPO levels over time (increase of similar to 1.4% relative to control) and, in comparison with MIRA clams (LAR: 17.7 nmol/g FW; MIRA: 11.4 nmol/g FW). After the depuration period, LAR clams recovered from the stress induced by CBZ. A decrease in LPO for LAR (decrease of similar to 40% in relation to the end of the exposure period) was accompanied by a decrease in CBZ tissue concentrations (decrease of similar to 61% relative to the end of the exposure period). MIRA clams were not oxidatively injured (low LPO levels remained unchanged after the depuration and CBZ decreased similar to 80% relative to the end of the exposure period). KW - Invertebrates KW - Pharmaceutical drugs KW - Biomarkers KW - Oxidative stress PY - 2017 DO - https://doi.org/10.1016/j.scitotenv.2016.12.069 SN - 0048-9697 VL - 580 SP - 1129 EP - 1145 AN - OPUS4-43297 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Almeida, Ângela A1 - Calisto, V. A1 - Esteves, V. I. A1 - Soares, A. M. V. M. A1 - Figueira, E. A1 - Freitas, R. T1 - Ecotoxicity of the antihistaminic drug cetirizine to Ruditapes philippinarum clams JF - Science of the Total Environment N2 - Cetirizine (CTZ) is an antihistaminic drug present in the aquatic environment, with limited information on its toxicity to organisms inhabiting this system. This study intended to evaluate the effects of CTZ on oxidative stress and energy metabolism biomarkers in the edible clam Ruditapes philippinarum after a 28 days exposure to environmentally relevant CTZ concentrations (0.0, 0.3, 3.0, 6.0 and 12.0 mu g/L). The results obtained showed that CTZ was accumulated by clams reaching maximum concentrations (up to similar to 22 ng/g FW) at the highest CTZ exposure concentrations (6.0 and 12.0 mu g/L). The bioconcentration factor (average maximum values of similar to 5) decreased at 12.0 mu g/L reflecting a reduction in clams uptake or increase of excretion capacity at this condition. The present study revealed that, in general, clams decreased the metabolic potential after exposure to CTZ (decrease in electron transport system activity), a response that led to the maintenance of glycogen content in organisms exposed to CTZ in comparison to control values. Our findings also showed that, CTZ did not exert significant levels of oxidative injury to clams. However, comparing the control with the highest exposure concentrations (6.0 and 12.0 mu g/L) a significant increase of the antioxidant enzyme superoxide activity (similar to 53 and similar to 44%) was observed in clams exposed to CTZ. Moreover, a tendency to increase lipid peroxidation (similar to 14 and similar to 9%) and carbonyl groups on proteins (similar to 11 and similar to 3%) was observed in clams exposed to CTZ (6.0 and 12.0 mu g/L) compared to control condition. Overall the present study suggests that toxic impacts may be induced in R. philippinarum if exposed for longer periods or higher CTZ concentrations. KW - Antihistamines KW - Clams KW - Biomarkers PY - 2017 DO - https://doi.org/10.1016/j.scitotenv.2017.05.149 SN - 0048-9697 VL - 601 SP - 793 EP - 801 PB - Elsevier B.V. AN - OPUS4-43311 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Almeida, Â. A1 - Calisto, V. A1 - Esteves, V. I. A1 - Soares, A. M. V. M. A1 - Freitas, R. T1 - Salinity-dependent impacts on the effects of antiepileptic and antihistaminic drugs in Ruditapes philippinarum JF - Science of the Total Environment N2 - In Coastal Systems, pollutants as pharmaceutical drugs exert changes from the molecular to the organism level in marine bivalves. Besides pollutants, Coastal Systems are prone to changes in environmental Parameters, as the alteration of salinity values because of Climate Change. Together, these Stressors (pharmaceutical drugs and salinity changes) can exert different threats than each Stressor acting individually; for example, salinity can change the physical-chemical properties of the drugs and/or the sensitivity of the organisms to them. However, limited Information is available on this subject, with variable results, and for this reason, this study aimed to evaluate the impacts of salinity changes (15,25 and 35) on the effects of the antiepileptic carbamazepine (CBZ, 1 (ig/L) and the antihistamine cetirizine (CTZ, 0.6 pg/L), when acting individually and combined (CBZ + CTZ), in the edible clam Ruditapes philippinarum. After 28 days ofexposure, drugs concentrations, bioconcentration factors and biochemical parameters, related to clam's metabolic caparity and oxidative stress were evaluated. The results showed that dams under low salinity suffered more changes in metabolic, antioxidant and biotransformation activities, in comparison with the remaining salinities under study. However, limited impacts were observed when comparing drug effects at low salinity. Indeed, it seemed that CTZ and CBZ + CTZ, under high salinity (salinity 35) were the worst exposure conditions for the dams, since they caused higher leveis of cellular damage. It Stands out that salinity changes altered the impact of pharmaceutical drugs on marine bivalves. KW - Muscheln KW - Salinität KW - Carbamazepin KW - Cetirizin KW - ELISA KW - Immunoassay KW - Antiepileptikum PY - 2022 DO - https://doi.org/10.1016/j.scitotenv.2021.150369 SN - 1879-1026 VL - 806 SP - 1 EP - 13 PB - Elsevier Science CY - Amsterdam AN - OPUS4-55561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Santos, S. A1 - Costa, C. A. E. A1 - Duarte, A. C. A1 - Scherer, H. W. A1 - Schneider, Rudolf A1 - Esteves, V. I. A1 - Santos, E. B. H. T1 - Influence of different organic amendments on the potential availability of metals from soil: A study on metal fractionation and extraction kinetics by EDTA JF - Chemosphere N2 - The effects of long-term application of different organic amendments, as compared to mineral fertilizer, on Zn, Cu and Pb content and leachability in a luvisol derived from loess were assessed. The organic fertilizers, applied since 1962, were compost (COM) – from green organic household waste, sewage sludge (SLU) – from municipal water treatment facilities, farmyard manure (FYM) and the doses applied since 1997 were 90 t ha-1, 10 t ha-1 and 9 t ha-1, once in 3 years, respectively. The kinetics of metals extraction with 0.05 mol dm-3 EDTA at pH 6.0 has been studied. The two first-order reactions model was fitted to the kinetic data and allowed to distinguish two pools for each metal: a 'labile' fraction (Q1), quickly extracted with a rate constant k1, and a 'moderately labile' fraction (Q2), more slowly extracted, with a rate constant k2. Simultaneously, the pseudo-total metal contents in the soil samples were determined after digestion with aqua regia (3:1 HCl + HNO3). The obtained parameters Q1, k1, Q2, k2, for the kinetics of extraction of each metal in the three replicates of each fertilization mode, as well as the pseudo-total metal contents, were statistically analysed. COM and SLU application resulted in an increase of the total contents of Pb, Zn and Cu in soil. Further, the percentage of labile Zn and Pb also increased in consequence of the application of those amendments, particularly COM. The increase was more noticeable for Zn. FYM, despite not increasing the total content of Pb, Zn or Cu, did also have an effect on the leachability of Zn and Pb, increasing their labile fraction in soil. These results point to a potential risk of increasing metals mobility in soil, mainly Zn, associated to the use of organic amendments, particularly COM or SLU. KW - Compost KW - Sewage sludge KW - Soils KW - Metal mobility KW - EDTA KW - Kinetics PY - 2010 DO - https://doi.org/10.1016/j.chemosphere.2009.11.008 SN - 0045-6535 SN - 0366-7111 VL - 78 IS - 4 SP - 389 EP - 396 PB - Elsevier Science CY - Kidlington, Oxford AN - OPUS4-22187 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -